JPS61265A - Fluorine-containing coating agent - Google Patents

Abstract

PURPOSE:To provide a fluorine-contg. coating agent which gives a coating film having excellent smoothness, lubricity, corrosionproofness, etc., containing a fluorine-contg. compd. in which a perfluoroalkyl group is introduced into the both terminals of an oligoethylene oxide group as an active ingredient. CONSTITUTION:A fluorine-contg. compd. (e.g., a compd. of formula II or III) in which a perfluoroalkyl group or a perfluoroalkenyl group is introduced into the both terminals of an oligoethylene oxide group of formula I (wherein Rf is a 4- 16C perfluoroalkyl, perfluoroalkenyl; A is a bivalent group other than oxygen; a is 0, 1; n is 0, 1-30) is prepd. Said fluorine-contg. compd. is used as a main component, and optionally a fluorine-contg. surfactant (e.g. a compd. of formula IV) or a fluorine-contg. amide compd. (e.g. a compd. of formula V) is added thereto to obtain the desired fluorine-contg. coating agent. The coating agent is suitable for use in coating metal, porcelain, glass, plastics, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fluorine-based coating material that has excellent smoothness, anti-friction properties, and anticorrosion properties, and more specifically, it relates to a fluorine-based coating material that has excellent smoothness, anti-friction properties, and anticorrosion properties.
This invention relates to a fluorine-based coating agent that forms a coating film with excellent properties as described above on solid surfaces such as glass and plastics.

Conventionally, various paints and coating materials have been used to protect the surfaces of metals, porcelain, glass, plastics, etc., but when particularly smooth surfaces are required, high-quality coatings are used in the coating phase. This is achieved by containing additives such as fatty acids, higher fatty acid esters, paraffinic hydrocarbons, silicone oils, dimethylpolysiloxane, dimethylpolysiloxane, and the like.

Furthermore, fluorine-containing polymers having fluorine-containing terminal groups in their side chains are also added to coating materials in order to improve the smoothness of the solid surface (Japanese Patent Application Laid-Open No. 126220/1983). Furthermore, fluorine-containing polymers having fluorine-containing terminal groups in their side chains are also used in paints themselves (%
No. 44).

On the other hand, recent advances in recording materials have been remarkable, especially in the field of magnetic tapes and magnetic disks, where performance has improved and recording wavelengths have become shorter, less than 2 μm, and in particular, lower noise levels and increased signal output are required. In addition to the composition of the magnetic layer, smoothing of the magnetic layer surface π(1) and reduction of friction are particularly required.

In addition, in order to improve the running performance of tapes and to reproduce still images clearly and over long periods of time in video tapes, we have also improved the smoothness, friction reduction, and durability of the protective coating for the magnetic layer. On the other hand, it is desired that the coating film be made thinner due to the need to express magnetic properties more sharply.

However, since conventional paints or coating materials containing smoothness improvers and fluorine-containing polymer coatings 1
The thickness of 1μ of the coating is usually 1 to 100μm, and reducing the thickness to a monomolecular 11 or 100μm diameter is important for the uniformity of the coating and the smoothness of the coating surface. Furthermore, there were problems such as a significant decrease in the strength of the coating film, making it extremely difficult.

The present inventors conducted intensive research to solve the problems of conventional protective coating films, and as a result, instead of the so-called fluorine-containing fJi combination, the present inventors introduced perfluoroalkyl groups at both ends of the oligoethylene oxide group. The fluorine-containing compound improves smoothness,
It has excellent friction reduction properties and also has excellent rust prevention properties on metal surfaces.
The present inventors have discovered that a thin and strong protective coating film can be formed, and have completed the present invention.

That is, the present invention provides a coating material containing a fluorine compound represented by the following general formula (I).

gr-+h in CH2CH20+CH, CH, O in CHz
CH2-(A clear Rf...(I) In the formula, Rf has 4 to 4 carbon atoms
16 perfluoroalkyl group or perfluoroalkenyl group, A is a divalent linking group that is not oxygen, and a is 0 or 1.
and n is 0 or an integer from 1 to 0.

In addition, Rf, A and a, which exist two each in one molecule,
Of course, it is not necessary that the two be the same.

In the fluorine compound according to the present invention, the Rf group has a par 70
is a loalkyl group or a per-70 loalkenyl group,
It may be linear, branched, cyclic, or a combination thereof, and may also have an oxygen atom interposed in the main chain, such as (CF3)2CFOCF2CF2-.

n is 0 or an integer from 1 to 0, and among these, 0 or an integer from 1 to 10 is particularly preferable.

ni l'i3 ).

-CH,CH,5CH2CH,C0N-l-CH2CH
2(J(2N-1-cH, cy, 5cH2cH2N-(
However, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
A hydroxyalkyl group, an alkenyl group, an alkyl group containing one or two ether oxygens, an aromatic group, or a group containing an aromatic group. ), -CB, CH□-,
-CH2CI(2CH,0-l-CH2CH2SCH2
CH20-1 crystal 3 l -CH2CH2S CH2CH,CO-, etc., but the fluorine-containing compound according to the present invention is as shown in the general formula (I),
Since it is especially important that Rf groups are bonded to both ends of the oligoethylene oxide group, it goes without saying that the present invention is not limited to the above-mentioned divalent linking group.

The fluorine-containing compound according to the present invention is already known and is produced by a certain method (for example, JP-A-58-49648).

You can also purchase commercially available products.

Specific examples of the fluorine-containing compound of the general formula [T] according to the present invention include the following.

C, F, 7+CH, CH2O1cH2CH2C6F,.

Consideration C6FIA model (J(,, CH2O horsetail CH2CH7
C, F, 3C, F, 7CM, CH20CH2CH, C5
F17CF3 CF3? Horse 7H・C,F,,CI,CH2CH7CH,OnCH2H2C
,F.

C1ff1F31 ← CH7 sho 04CH7CH20 medium CH
2), Cl51! '31C7F154CH2 people () ÷
CH2CH2OCH2CH20 loaf-lff1F3+c,
F,, -(-CH2 No. 0-←CH2CH2O ACH2
Clam C9F+9喌喀I C+aF27+CHz sweat 0-+CH2CH2O back season H2
No. CI8”2□C,F,, CH2CH,S CH2C
H2O-(-CH2CH20% CH, CH25CH,
,0H2C,F,.

C,,F2. CH2CH25CH2CH7O-(CH2
CH,,O dirt CH2CH25CH2CH,C,,F2.
.

C9F+9CH25CH2 rule C smell: l'H2CH,O
Dirt CCH2CH25CH2CH2C,F.

In the present invention, the aforementioned fluorine-containing compounds may be used alone or in a mixture of two or more types, but it is also possible to use fluorine-containing surfactants known in the art or JP-A-58-213
It can be used in combination with the so-called fluorine-containing amide compound described in No. 057. Fluorine-containing surfactants or fluorine-containing amide compounds that can be used in combination can be selected from a wide variety, but the composition containing them as a component is itself applied to a solid surface as a composition for compensation. Therefore, it is preferable to have a wax-like or solid form at least at a constant width, and a substance having a high melting point is more preferable.

Typical fluorine-containing surfactants include the following A:
-D group, but the present invention is not limited to these.

(Group A) General formula [A] R'f-X, -8o3M...
[A-1], R'(Y+ C00M - [A 2
] or (n,'f-z-)-jp(OM)3-j
...[A-3,], where R'f represents a perfluoroalkyl group or a perfluoroalkenyl group having 4 to 20 carbon atoms (some hydrogen atoms may remain)7. X,
is +C1 (29-3, -0 combined CH, right -1 or 10-0÷CH,,) - (here, p represents an integer from 1 to 20.

, M is an alkali metal, -NH amine salt, hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Y is +CH→
1, R' -N+cpr2+ (where p is as defined above, R' represents hydrogen or an argyl group having 1 to 6 carbon atoms), and R' -GCH2-)-,0-eCH2-CH -0+ or is the same as above, R1 is a hydrogen atom or has 1 to 1 carbon atoms
4 represents an alkyl group, g represents an integer from 1 to 50,
R" (-CH, -CH-0)-g contains R"4CH2CH7"0)g+ 4CH2CHO+g2, (
g+ 10g2=g) shall also be included. ), and j is an integer of 1.2 or 3.

Specific examples of the compound of general formula [A] include the following.

C, F, 3SO3Li, C6F,, So! IK
, C6F,, SO3'NH,, C8F, 7801
Li, C, IF, 7SO3Na %C8F, 7S
O3K.

, 5o3NH4, C7 澹Coo(CH2)
3SO, to C,F,,C00NHJ H(CF2)IOCOOH,C,1)F'2. (CH,
), (,COONa.

C2H, C3H7 C, F, 3SO2N-CH2CH20P C8F, □5
o2NCH2COOK.

OC2H, C211゜I I C7F, 5-C-N-CH2-COONa, cln, F
ll)-N-CH2CH20゜11)I C6F,,CH2CH20P(OI(),,C6F13
CH2CH20P (ONa)2, OO I111 C8F, 7CH2CH20P(OH)2, (C8FI?
CH2C) (20)2 P(OH)2, C3H70C
2H.

5o2NCH2CH20P(OH),,C8F,, 5
o2N4CH2CH2-)-PL(JK)2, Cnl
'I'l7b02N-CH2CH20(-CH2CH-
0 sho C8F, 7-C-0-(CH2CH20-), P
(0-NH4)2,CH,,OC,oF2. CH2-0+CH2CHO)-5P(OK
)2 or c6F13 However, , R'f has the same meaning as above, and U is punishment -(D←R' (-CH2+--0-C))-8o2-N(-CH29, -0 (-CH29% R' or -802N 4 CH2')-pO(nee CH
4 (R', R'' and psg have the same meanings as above, and U and either R4, R5 or R6 may be cyclic), and R4.

R3 and R6 are a hydrogen atom, an alkyl group having 1 to 1 o carbon atoms, a hydroxyalkyl group, a cycloalkyl group, or an aralkyl group having 7 to 15 carbon atoms, and X2 is a halogen atom, H8O4, -CR3-S O4, -H2PO4,
-QC-CH, or -8O3-JC)-CH3.

Specific examples of the compound of general formula [B] include the following.

C7°F,, -o-/C)-cH24cH,)3C5c
, F, □o-(Σ5o2Nll-CI, Cl2N (
CHs)p C1l s c+o F+a O('-
CHz CH2O included. CH, CH2N” (CHen), T
oi C,F,78-NH-(C1f2)3-N"'N
-(CH,), I, C, F, 7So, NH-(-
CH2)”, N (CH,)30.5(ycH,,C6
F,,,5o2NH-(C'H2)0-(CH,),N
"etc. R" (Group 0) General formula [C"l R'fV 4 CH2CH2
+gRs CC1] In addition, R'f is the same as above, ■ is a simple bond or a bonding group (herein, R' has the same meaning as above), and R'', gsR3 and Z have the same meanings as above, r and S are each an integer of 0 or more, although they are not 0 at the same time, and W is 1
isocyanate compound residue having a valence of 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloargyl group, an aralkyl group having 7 to 15 carbon atoms, or at least one benzene ring. L is a residue of a compound containing any alcoholic hydroxyl group, and L is a monovalent residue of an aliphatic, alicyclic or aromatic monoalcohol, polyalkylene Ether glycol, blocked polyoxyalkylene ether/l/f glycol, polyester glycol or divalent residue of polymethylene glycol (one side of these glycols may be an alkyl etherified monovalent residue), trimethylolpropane It represents a polyvalent residue of hexavalence or higher, such as oxydialkyl L'7 adduct of pentaerythritol or pentaerythritol.

Specific examples of the compound of general formula (C) include the following.

Ca F 13 CH2CH20H, Cn F I?
O(CH2CH20), + CH,! .

OC2H.

Cl2F2!1-C04CH2CH2-0+8H,C8
F,,5o2N(CH2CH2C3H70 04H%C8F,So2M-(CH,CH2O7IL
c, p',, c -C2H, C2H.

N+CH,CH,O輻I(,C,oF,, -N-CH
, CH20H.

CM.

I NH-C-0-FCH2CH20)CH,,C,,F,
, -0-OH2CH20-CCH.

cH.

CH.

C3H1 CH2CH20H, 7C8, etc. However, R'f, U, R4, R3 are as described above, k is an integer from 1 to 4e θ e, and A is an anionic group such as -C00 or -So. It is.

Specific examples of compounds of general formula CD are as follows.

O c,F,3cNm<CH2)J”(cH,>2cn2c
ooe, C, F, 7CNH(CH2)sN”(CH3
)2 (CH2)3COOe, C8°F,. OQω
e CH2N (CH,)2CH2Coo % C,F,
70÷CH2CH2O+(CH2)2N (CH3)P
(CH2)2COOe, CIOFllll-08 ■ ■ 0 8O7NH (CH7)3N (CH3)2 (CH2)
sSO3,C,F1□ω e So,NH(CH2)3N ((j(3)2(CH2)
3So, ,C,F,,5o2(g)
■N (CH2CH20H),
(CH2)2COO, C5FnSO2NH(CH2)s
(g) e O(CHJ2N ((:HJtCH2COO or a fluorine-containing amide compound) is a compound represented by the general formula (■). In the formula, R″f is half/l/ having a carbon number of 4 to 2 o. , +1-0 alkyl group is a perfluoroalkenyl group, preferably a perfluoroalkyl group or a perfluoroalkenyl group having 4 to 16 carbon atoms.

, Q is -co-1+CHiSO2-1+CH4C0-(
However, i is an integer from 1 to 8), preferably -
co-1-so2-.

R1 and R2 are a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, where m and n are integers of 1 to 2 o, and R3 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and % R
It may be the same as or different from I%R2. ), preferably,
The actual size of hydrogen or an alkyl group having 01 to 20 carbon atoms is preferable.

A typical example of these stones is the 17th stone.

C,F,7So2NH,,C,F,7So,'NHC,
H,,C,F,7So2NHOCH.

C,F,3CNCH2CH,OH,C8F,7So2N
(CH2C) (20H),,C2H.

C,F,3So,N(CH,CH,0H)2,C,F,
,5o2NCH3CH7OH.

C2H.

C8F,,5o2NCH2CH20H,C8F,7CM
2CH, 5o2NT (2 or C8F, 7CH2CH,
Examples include C0NH-C4H11.

There is no restriction on the amount of the fluorine-containing surfactant or fluorine-containing amide added to the fluorine-containing compound (general formula (I)) according to the present invention, but it is usually 0 to 60% based on the fluorine-containing compound. weight%, preferably 5 to 6OW, weight%.

There are no restrictions on the coating and coating method of the coating material of the present invention, but usually the compound of the general formula CI) is dissolved in an appropriate solvent to a concentration of IX10'' to 10X9, and a dipping method is used. ,
It is applied to the substrate using a spray method or the like. Further, if necessary, it is possible to form a uniform and thin coating by drying, heating or puffing the coated surface.The thickness of the coating film at this time is 100A to 100μm.

There are no restrictions on the organic solvent used for coating by dipping, spraying, etc., but among the fluorine-containing compounds represented by the general formula (I), those with n smaller than 10, and those of the general formula ( Since the water solubility of the fluorine-containing amide compound represented by II) is not very good, it is preferable to use an organic solvent.Although a solvent may be used alone, a mixed system of water and an organic solvent or a combination of organic solvents is preferable. Mixed systems are also preferably used. Examples of these organic solvents include alcohols such as methanol, ethanol, gropanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, needles such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran, and ethyl acetate. , esters such as butyl acetate, halogenated hydrocarbons such as dichloromethane, trichloroethane, trichlorofluoromethane, etc.

As mentioned above, the coating material of the present invention can be used as a protective coating layer on various solid surfaces, such as a moisture-proofing and rust-proofing agent, an antifouling agent, a lubricant, an antistatic agent, an anti-friction agent, a release agent, a mold release agent, etc. However, taking advantage of the thinness and smoothness of the coating film, it is particularly suitable for coating the magnetic layer of magnetic recording products in the field of recording materials.

Solids to be applied include, for example, copper, aluminum,
Non-magnetic metals such as zinc and polyethylene terephthalate,
It is deposited on polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polypropylene, cellulose derivatives such as cellulose acetate, plastics such as polycarbonate-1, and in some cases ceramics such as glass, porcelain, and earthenware. ferromagnetic alloy (
Items whose main components are iron, cobalt and/or nickel, with small amounts of aluminum, silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earth metals, etc.)
Alternatively, a ferromagnetic base made by vapor-depositing iron or chromium in the presence of a certain amount of oxygen (by using it as a protective coating for a magnetic layer made of tetraoxide, the surface of a magnetic tape or magnetic tape containing the same can be smoothed. It is expected that the magnetic properties will be improved and the magnetic properties will be more sensitive due to the thinner coating.

On the other hand, the present agent can form a transparent, smooth, and thin coating film on the glass surface, so it can be used for applications that require oil resistance and extraction resistance, such as oil stain prevention agents for various optical equipment. It can also be used to imitate.

Next, Examples and Comparative Examples of the present invention will be explained in detail, but it goes without saying that the present invention is not limited in any way by such explanations.

In addition, in the following examples, 91i and comparative examples, the average R acidity of the surface coating film was measured using an optical Y-mouth microscope with a magnification of 160 times to check for the presence or absence of bumps on the coating surface. , 5 levels (5: Not at all, 4: Slight bumps on the surface, 3: Slight bumps on the surface, 2: Slight bumps on the surface, 1: Slight bumps on the surface.
Evaluation was made using the following criteria: "There are some problems with everything" (the higher the number, the better).

The contact angle was determined by dropping 6 μl of n-decane onto Measurement Table 1, and using a contact angle measuring device including a goniometer manufactured by Elma, at 25° C.

The salt water resistance test was carried out in a sealed box made of polyvinyl resin.
Drop 25 μl of artificial seawater onto the 4th surface of the l-t, observe the time until it starts to become cloudy due to rust, and rate it in 5 stages (5: 5 hours or more, 4: 6 to 5 hours, 3: 2 to 6 hours, 2: 1-2
time, 1:1 hour or less).

The antistatic performance test was conducted using 1 oc of commercially available polyester film (Epik Film +400: trade name manufactured by Kimoto Co., Ltd.).
For the sample coated and dried on a rnx107 section, the state of decrease in surface potential on the treated surface was measured using the high static pressure zone measurement method. To prepare a sample, a polyester film section is immersed in the solution, air-dried, and then stored in a container adjusted to a relative humidity of 40% for 24 hours or more. The obtained sample was measured using an electrostatic paper analyzer (Model 5P-428 manufactured by Kawashi Ichiichi Ichiki Seisakusho) installed in a room controlled to a relative humidity of 40%. 4111 constant method is during application; H--6
A KV was applied to the surface of the sample, and changes in surface position were continuously recorded for 1 minute. The measurements were repeated using three samples of the same treatment, and the average value of I-1 was determined.

#Rejection Resistance 11i: Tan effect vermilion was evaluated by preparing polyester film samples in the same manner as in the case of antistatic performance, and comparing the dynamic friction divisor between treated surfaces. The measurement of the error coefficient was carried out using a friction test jig manufactured by Toyo Baldwin Co., Ltd. according to a method according to the American Dramatic Materials Testing Association Standard 1)-1894 (weight weight = 2669, tensile strength: 100 am
/min).

Examples 1 to 10 and Comparative Examples 1 to 5 The isobutyl alcohol/7 Leon-113 (1: IV/V) solution of each sample A1 to 15 shown in Table 1 was dropped onto a microslide glass (76 x 26 mm), Table 1 shows the results of determining the surface smoothness and the contact angle with n-decane after drying for 3 minutes.

Examples 11 to 20 and Comparative Examples 6 to 10 Table 2 shows the results of the wall water resistance test using sample plates coated with 461 to 15 samples on superfinished steel plates and dried during filtration. Show the results.

Table-2 The sample numbers are the same as those in Table-1.

Examples 21-60 and Comparative Examples 11-15 Table 6 shows the results of the antistatic performance test for Samples/I61-15.

Table-6 The sample numbers are the same as those in Table-1.

Examples 51 to 40 and Comparative Examples 16 to 20 Table 4 shows test results regarding the frictional resistance reduction effect of Samples 1 to 15.

Table-4 The sample numbers are the same as those in Table-1.

The compounds of Examples 41 to 450 were tested for smoothness, contact angle, salt water resistance, antistatic property, and frictional resistance reducing property according to the same method as in the above Examples. The results are summarized in Table 59.

As shown in Table 5, similar to the compound where a is 1, a is 0.
The compound also showed excellent performance.

Procedural amendment (voluntary) July 6, 1980 Director General of the Japan Patent Office Manabu Shiga 1 Indication of the case 1982 Patent Application No. 119103 2 Name of the invention Fluorine-based coating agent 6 Case of person making supplements Tono Seki 1 Ito Patent applicant: 35-58 Sakashita 3-chome, Itabashi-ku, Tokyo 174 (28
8) Inu Nippon Ink Chemical Industry Co., Ltd. Representative Kawa
Kuni Mura Shigeru 4, Agent: Dainippon Ink and Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Detailed explanation of the invention in the specification? Column , :hi(・ :'
, j:', l.

6 Contents of amendment (11 Specification, page 12, line 3 [”c, p, , cH2cH2scH7cH2d O+C
H2CH2CCH)C1(7SCH7CH2C7F,
,] is corrected.

(2) [”C,F,,CH2CH25CI(2CH2C-0+
CH2CH7O village. ccn2cH2sca2cH7c,
Correct F, J.

(3) rnso4, 2nd line to 1st line from the bottom of page 18,
-CH3-8o4, Oll0 -H2PO,, -CH3Co or CH,, Os
o, Q. ” he corrected.

(4) The column for fluorine-containing compounds of Example 1 on page 65 of the same page (
that's all)

Claims (1)

[Claims] General formula [I] Rf-(A)-_aCH_2CH_2O-(CH_2C
H_2O)-_nCH_2CH_2-(A)-_aRf
... [I] [In the formula, Rf is a perfluoroalkyl group or perfluoroalkenyl group having 4 to 16 carbon atoms, A is a divalent linking group that is not oxygen, and a is 0 or 1, , n is 0 or an integer from 1 to 30. ] A coating material containing a fluorine-based compound represented by: